CN113087629A - Preparation method of 1, 5-dichloro-2, 4-dinitrobenzene - Google Patents
Preparation method of 1, 5-dichloro-2, 4-dinitrobenzene Download PDFInfo
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- CN113087629A CN113087629A CN202110374481.2A CN202110374481A CN113087629A CN 113087629 A CN113087629 A CN 113087629A CN 202110374481 A CN202110374481 A CN 202110374481A CN 113087629 A CN113087629 A CN 113087629A
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- temperature
- dinitrobenzene
- dichloro
- sulfuric acid
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- ZPXDNSYFDIHPOJ-UHFFFAOYSA-N 1,5-dichloro-2,4-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC([N+]([O-])=O)=C(Cl)C=C1Cl ZPXDNSYFDIHPOJ-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- ZPQOPVIELGIULI-UHFFFAOYSA-N 1,3-dichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1 ZPQOPVIELGIULI-UHFFFAOYSA-N 0.000 claims abstract description 10
- TYNVOQYGXDUHRX-UHFFFAOYSA-N 1-nitropyrazole Chemical compound [O-][N+](=O)N1C=CC=N1 TYNVOQYGXDUHRX-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 5
- 238000010907 mechanical stirring Methods 0.000 claims abstract description 5
- 230000000802 nitrating effect Effects 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000007787 solid Substances 0.000 claims abstract description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 abstract 2
- WDCYWAQPCXBPJA-UHFFFAOYSA-N 1,3-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC([N+]([O-])=O)=C1 WDCYWAQPCXBPJA-UHFFFAOYSA-N 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 238000010792 warming Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 7
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 4
- 238000006396 nitration reaction Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- KMAQZIILEGKYQZ-UHFFFAOYSA-N 1-chloro-3-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC(Cl)=C1 KMAQZIILEGKYQZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 125000006414 CCl Chemical group ClC* 0.000 description 1
- IKCHGEHXCSIRPW-UHFFFAOYSA-N ClC1=CC(=CC=C1)Cl.[N+](=O)(O)[O-] Chemical compound ClC1=CC(=CC=C1)Cl.[N+](=O)(O)[O-] IKCHGEHXCSIRPW-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- ZODDGFAZWTZOSI-UHFFFAOYSA-N nitric acid;sulfuric acid Chemical compound O[N+]([O-])=O.OS(O)(=O)=O ZODDGFAZWTZOSI-UHFFFAOYSA-N 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/08—Preparation of nitro compounds by substitution of hydrogen atoms by nitro groups
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开了一种1,5‑二氯‑2,4‑二硝基苯的制备方法，以间二氯苯为原料，N‑硝基吡唑和H2SO4为硝化剂制备1,5‑二氯‑2,4‑二硝基苯；具体包括如下步骤：取98％的硫酸8ml于四口瓶中，在机械搅拌，温度为20℃条件下，向浓硫酸中滴加间二氯苯0.012mol，加料完成后，水浴升温至60℃，于此温度下将N‑硝基吡唑0.024mol平均分四份依次加入，加料过程反应体系会出现升温现象，待温度降为初始温度后再次加料，加料完成保持搅拌，65℃恒温反应6h，趁热将反应液倒入装有冰块的容器中并搅拌使溶液温度降为5℃，有固体悬浮物析出。
The invention discloses a preparation method of 1,5-dichloro-2,4-dinitrobenzene. Meta-dichlorobenzene is used as a raw material, and N-nitropyrazole and H 2 SO 4 are used as nitrating agents to prepare 1, 5-dichloro-2,4-dinitrobenzene; specifically includes the following steps: take 8ml of 98% sulfuric acid in a four-necked flask, and under mechanical stirring at a temperature of 20°C, add m-dinitrobenzene dropwise to the concentrated sulfuric acid. Chlorobenzene 0.012mol, after the feeding is completed, the water bath is warming up to 60°C, at this temperature, N-nitropyrazole 0.024mol is added in four equal parts in turn, and the reaction system will heat up during the feeding process, and the temperature is reduced to the initial temperature. Then add the material again, keep stirring after the addition, and react at a constant temperature of 65 °C for 6 hours. Pour the reaction solution into a container with ice cubes while it is still hot and stir to reduce the temperature of the solution to 5 °C. Solid suspended matter is precipitated.
Description
Technical Field
The invention relates to the field of compound preparation, and particularly relates to a preparation method of 1, 5-dichloro-2, 4-dinitrobenzene.
Background
The 1, 5-dichloro-2, 4-dinitrobenzene is mainly used as an intermediate for organic synthesis and also has application in auxiliaries, pesticides and medicines. 1, 5-dichloro-2, 4-dinitrobenzene has an important role in organic synthesis, the market of the product is always good, and the development of the product has good economic and social benefits.
At present, the 1, 5-dichloro-2, 4-dinitrobenzene is prepared by taking m-dichlorobenzene as a raw material and performing high-temperature nitration in a nitration system of mixed nitric acid and sulfuric acid. US005574188A discloses that the use of a fuming sulfuric acid-nitric acid system to nitrate 1, 3-dichlorobenzene gives an 89.8% yield; lepeng (Lepeng. preparation of intermediate RH1658 herbicide [ D ]. Shenyang university of industry, 2007.) in its Master paper 59.5g of m-dichlorobenzene was reacted at 110 ℃ for 3 hours by a mixed acid system of nitric and sulfuric acid at 100 ℃ with a reaction yield of 95%. However, the method has the disadvantages that the reaction temperature is high, and fuming nitric acid-concentrated sulfuric acid can generate a large amount of nitrogen oxide gas and excessive waste acid to cause environmental pollution.
Disclosure of Invention
In order to solve the problems, the invention provides a preparation method of 1, 5-dichloro-2, 4-dinitrobenzene.
In order to achieve the purpose, the invention adopts the technical scheme that:
a process for preparing 1, 5-dichloro-2, 4-dinitrobenzene from m-dichlorobenzene as raw material and N-nitropyrazole and H2SO4Preparing 1, 5-dichloro-2, 4-dinitrobenzene for a nitrating agent; the method specifically comprises the following steps: taking 8ml of 98% sulfuric acid in a four-mouth bottle, mechanically stirring, dropwise adding 0.012mol of m-dichlorobenzene into concentrated sulfuric acid at the temperature of 20 ℃, heating in a water bath to 60 ℃ after feeding, uniformly adding 0.024mol of N-nitropyrazole in four parts at the temperature, wherein the reaction system is heated in the feeding process, feeding again after the temperature is reduced to the initial temperature, stirring after feeding is finished, reacting at the constant temperature of 65 ℃ for 6 hours, pouring the reaction solution into a container filled with ice blocks while the solution is hot, stirring to reduce the temperature of the solution to 5 ℃, and separating out solid suspended matters.
Further, the rotation speed of the mechanical stirring is 300-400 rpm.
The invention has the following beneficial effects:
the invention provides a preparation method of 1, 5-dichloro-2, 4-dinitrobenzene. According to the preparation method, N-nitropyrazole and sulfuric acid are used as nitration reagents, m-dichlorobenzene is directly nitrated to obtain 1, 5-dichloro-2, 4-dinitrobenzene, the raw material source is rich, the cost is low, the mixed acid of nitric acid and sulfuric acid is avoided being used as a nitrating agent, no pollution gas nitrogen oxide is generated in the reaction process, no waste acid is generated, and the environmental pollution is small; furthermore, the preparation method provided by the invention has the advantages that the nitration reaction is carried out at the temperature of 65 ℃, the reaction condition is mild, the long-time reaction at high temperature is not needed, the requirement on reaction equipment is low, the purification is easy, and the purity of the obtained product is high.
Drawings
FIG. 1 is a synthetic scheme of a process for preparing 1, 5-dichloro-2, 4-dinitrobenzene according to an embodiment of the present invention.
FIG. 2 is an infrared spectrum of the target product prepared in example 1 of the present invention.
FIG. 3 is a high performance liquid chromatography of the target product prepared in example 1 of the present invention.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
Example 1
The embodiment of the invention provides a preparation method of 1, 5-dichloro-2, 4-dinitrobenzene, wherein m-dichlorobenzene is taken as a raw material, N-nitropyrazole and H2SO41, 5-dichloro-2, 4-dinitrobenzene is prepared for a nitrating agent, and the synthetic route is shown in figure 1; the method specifically comprises the following steps: taking 8ml of 98 percent sulfuric acid into a four-mouth bottle, dropwise adding 0.012mol of m-dichlorobenzene into concentrated sulfuric acid under the condition of mechanical stirring (300 plus 400 rpm) at 20 ℃, heating to 60 ℃ in a water bath after feeding, adding 0.024mol of N-nitropyrazole in batches at the temperature (the reaction system can be heated in the feeding process, and feeding is carried out again after the temperature is reduced to the initial temperature), keeping stirring after feeding, reacting at the constant temperature of 65 ℃ for 6h, pouring the reaction solution into a container filled with ice blocks while the solution is hot, stirring to reduce the temperature of the solution to 2 ℃, separating out solid suspended matters, refining by using ethanol after suction filtration and water washing, wherein the yield is 50.6 percent, the melting point of the product is measured by an X-4B micro melting point instrument: 101-103 ℃ (article value 101-104 ℃). The product is judged to be 1, 5-dichloro-2, 4-dinitrobenzene.
Table 1 results of elemental analysis of the target product of example one
The target product was subjected to elemental analysis and found to be 1, 5-dichloro-2, 4-dinitrobenzene as shown in Table 1, which showed that the measured values and the calculated values were substantially matched.
TABLE 1 elemental analysis results of the target products
FIG. 2 is an infrared spectrum of the target product prepared in example 1, with the following data:
IR(KBr,v cm-1)3088cm-1、1411cm-1there are absorption peaks, which indicate the presence of benzene ring, 900, 887, 818m-1Is the peak position of C-Cl; at 1571cm-1、1322cm-1Has strong absorption peak, and is proved to have C-NO2Is present.
FIG. 3 is a high performance liquid chromatography of the target product prepared in example 1 of the present invention;
chromatographic conditions are as follows: preparing solution containing target substance with acetonitrile and 0.1% acetic acid at flow rate of 1.0 mL/min-1The ultraviolet absorption wavelength is 260nm, and the sample injection amount is 20 mu L. As shown in FIG. 3, the retention time of the target product was about 11.22min, and the purity of the product was 98.5% by area normalization.
In summary, the molecular structure of the measured target product is consistent with the molecular structure of m-nitrochlorobenzene, that is, the target product obtained in the embodiment 1 of the present invention is m-nitrochlorobenzene, and the purity of the product is 98.5%.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes or modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention. The embodiments and features of the embodiments of the present application may be combined with each other arbitrarily without conflict.
Claims (3)
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| CN202110374481.2A CN113087629A (en) | 2021-04-07 | 2021-04-07 | Preparation method of 1, 5-dichloro-2, 4-dinitrobenzene |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202110374481.2A CN113087629A (en) | 2021-04-07 | 2021-04-07 | Preparation method of 1, 5-dichloro-2, 4-dinitrobenzene |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102173993A (en) * | 2011-03-09 | 2011-09-07 | 南通市天时化工有限公司 | Method for synthesizing 4,6-diamino resorcinol dihydrochloride (DAR) |
| WO2012088190A1 (en) * | 2010-12-20 | 2012-06-28 | E. I. Du Pont De Nemours And Company | 2,4,5-triaminothiophenols and related compounds |
| CN110627738A (en) * | 2019-10-23 | 2019-12-31 | 浙江南郊化学有限公司 | Synthetic method of pesticide intermediate for synthesizing flumioxazin |
-
2021
- 2021-04-07 CN CN202110374481.2A patent/CN113087629A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012088190A1 (en) * | 2010-12-20 | 2012-06-28 | E. I. Du Pont De Nemours And Company | 2,4,5-triaminothiophenols and related compounds |
| CN102173993A (en) * | 2011-03-09 | 2011-09-07 | 南通市天时化工有限公司 | Method for synthesizing 4,6-diamino resorcinol dihydrochloride (DAR) |
| CN110627738A (en) * | 2019-10-23 | 2019-12-31 | 浙江南郊化学有限公司 | Synthetic method of pesticide intermediate for synthesizing flumioxazin |
Non-Patent Citations (2)
| Title |
|---|
| GEORGE A. OLAH,ET AL.: "Aromatic Substitution. 47. Acid-Catalyzed Transfer Nitration of Aromatics with N-Nitropyrazole, a Convenient New Nitrating Agent", 《JOURNAL OF ORGANIC CHEMISTRY》 * |
| 刘殿卿 等: "普莱克尼啶中间体9-甲基-2,4-二硝基-5-氯吖啶的合成", 《化学研究与应用》 * |
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